Occurrence of per- and polyfluorinated compounds in paper and board packaging materials and migration to food simulants and foodstuffs.

This work describes the screening of twenty three per- and polyfluoroalkyl substances (PFASs) in twenty five paper and board (P/B) packaging materials and their migration to several food simulants (50% ethanol, 95% ethanol and Tenax®) at different conditions of time and temperature. A different migration pattern depending on the carbon chain length was observed; while short carbon chain PFASs tend to migrate more to 50% ethanol than to 95% ethanol, long chain PFASs showed the opposite trend. On the other hand, very low migration percentages of all PFASs to Tenax® were found. Finally, migration of 9 PFASs into real foods (cereals, rice and infant milk powder) for 6 months was quantified and compared with the results obtained with the simulants. As a result, significant underestimations of the PFASs migration to foodstuffs were obtained using Tenax®, especially for short carbon chain PFASs and milk powder.

Wine markers in archeological potteries: detection by GC-MS at ultratrace levels.

The detection of organic residues that remain absorbed into the pores of ceramic artifacts constitutes a source of information regarding their management. Taking into account the poor conservation state of the potteries and the low amount of the organic tracers together with the main drawbacks to get the relevant information concerning different aspects of past societies, the detection of organic biomarkers is still an analytical challenge. In this work, an improved analytical methodology to maximize the recovery of organic markers related to wine in archeological ceramics is presented. The developed method consists on the extraction of wine-related organic compounds including tartaric acid, malic acid, fumaric acid, succinic acid, citric acid, and syringic acid by means of ultrasonic probe-assisted extraction (UPAE) followed by a preconcentration step by mixed-mode strong anion exchange and reversed-phase solid-phase extraction (SPE) and a derivatization step prior to analysis by means of gas chromatography-mass spectrometry (GC-MS). Finally, the method was applied to real archeological ceramic fragments (two dolia), suspected to have been used to store wine, together with organic residues found inside two amphorae from Zaragoza (Spain). Graphical abstract.

Mixed-mode SPE followed by GC-MS analysis to determine water soluble organic compounds in aerosol and historical mortars affected by marine atmosphere: The case of Punta Begoña Galleries (Getxo, North of Spain).

This work describes the development of an analytical procedure for the determination of short chain dicarboxylic acids (C2-C10) both in aqueous and solid matrices such as aerosols and mortars. The developed and validated methodology was based on the preconcentration of compounds by means of mixed-mode solid phase extraction and gas chromatography-mass spectrometry, regardless the analyzed samples. In the case of solid samples, a prior extraction of target compounds using ultrasonic probe-assisted solid-liquid extraction was required. In general terms, the developed procedure rendered good results in terms of accuracy (apparent recoveries in the range 90-130% and 86-98% for marine aerosol and mortar samples, respectively) and repeatability (%RSD < 25%) except for those compounds interacting more strongly with the solid matrix and being more reactive. The method was applied to detect dicarboxylic acids in marine aerosol water samples and in mortars of a 20th century historical building (Punta Begoña Galleries, Getxo) located in a coastal environment (Biscay Gulf, Basque Country, Northern Spain) with industrial activity. According to the results, harbor activities may have effect on the concentrations of dicarboxylic acids found in both matrices since the façade of the building exposed to the industrial harbor (southwest orientation) appears to be more contaminated than the one oriented to the northwest.

An alternative analytical method based on ultrasound micro bath hydrolysis and GC-MS analysis for the characterization of organic biomarkers in archaeological ceramics.

The analysis of organic biomarkers in ancient and valuable archaeological remains provides a worthwhile source of information regarding their management. This work was focused on the development of an analytical procedure to characterize organic residues that have remained in archaeological ceramic samples. A novel analytical approach based on an alkaline hydrolysis by means of an ultrasound micro bath followed by liquid extraction was proposed to isolate saturated and unsaturated fatty acids, degradation products such as dihydroxy acids or dienoic fatty acids, isoprenoid fatty acids, and many other biomarkers from archaeological remains. This main goal has been achieved after the optimization of the main parameters affecting the hydrolysis step, the extraction procedure, and the derivatization step prior to the gas chromatography-mass spectrometry analysis. In this work, archaeological ceramic remains suspected to have been used by Basque Whalers to store whale oil in the period from the sixteenth to the seventeenth century were studied. Nevertheless, the proposed method is useful to determine the organic remains preserved in many other archaeological ceramic remains. Moreover, this methodology can be used to determine organic remains in any porous ceramic, archaeological or not. The preliminary results of the analysis of ceramic vessels led to the determination of some interesting unsaturated compounds such as 11-eicosenoic acid, an important biomarker of marine commodities, and several saturated fatty acids, which could be indicative of having used the vessels to store whale oil. Graphical abstract ᅟ.

Assessment of commercially available polymeric materials for sorptive microextraction of priority and emerging nonpolar organic pollutants in environmental water samples.

Among the different organic pollutants, persistent organic pollutants and emerging organic contaminants (EOCs) are of particular concern due to their potentially dangerous effects on the ecosystems and on human health. In the framework of the analysis of some of these organic pollutants in water samples, sorptive extraction devices have proven to be adequate for their monitoring. The efficiency of four commercially available and low-cost polymeric materials [polypropylene, poly(ethylene terephthalate), Raffia, and polyethersulfone (PES)] for the simultaneous extraction of 16 organic compounds from five different families from environmental water samples was evaluated in this work. Firstly, the homogeneity of the sorbent materials was confirmed by means of Raman spectroscopy. After the optimization of the parameters affecting the extraction and the liquid desorption steps, it was found that PES showed the largest efficiencies for slightly polar analytes and, to a lesser extent, for nonpolar analytes. Additionally, Raffia rendered good extraction efficiencies for nonpolar compounds. Thus sorptive extraction methods followed by large volume injection-programmable temperature vaporizer-gas chromatography-mass spectrometry were validated using PES and Raffia as sorbent materials. The validation of the method provided good linearity (0.978 < r (2) < 0.999 for PES and 0.977 < r (2) < 0.999 for Raffia), adequate repeatability (below 19 % and 14 % for PES and Raffia, respectively), and low method detection limits (low ng · l(-1) level). Finally, these materials were applied to the analysis of contaminants in environmental water samples.